Animalization of cellulose



dyed with an acid dye.

ANIIVIALIZATION F CELLULGSE Edward L. Kropa, Greensboro, N.C., assignor to American Cyanarnid Company, New York, N.Y., a corporation of Maine N0 Drawing. Filed Dec. 9, 1957, Ser. No. 701,321

12 Claims. (Cl. 8-117) The present invention relates to the dyeing of cellulosic materials and more particularly to the process for rendering cellulosic materials susceptible to or dyeable by acid dyestufis (which contain the color in the anion) of the type usually employed in the dyeing of wool.

As is generally well recognized in the textile dyeing industry, those dyes which are normally employed in the dyeing of cellulosic materials, as for example, cotton, rayon and the like, are not suitable for the dyeing of textile materials such as wool, silk and nylon, and certain of the synthetic fibers, such as acrylic fiber. Conversely, the dyes normally employed for purposes of dyeing textile materials of the latter classes are normally not suitable for the dyeing of cellulosic fibrous materials, such as, for example, cotton and regenerated cellulose, such as rayons and the like.

It is an object of the present invention to provide a process whereby cellulosic materials may be pre-treated in a convenient and economical manner so as to be susceptible to the acid dyestuffs of the type normally employed in the dyeing of wool.

It is a further object of the present invention to provide a process for dyeing cellulosic materials in which the specific aspect of pre-treatrnent is an integral part of the process.

These and other objects and advantages of the present invention will bwome more apparent from the detailed description set forth hereinbelow.

In accordance with the present invention, a process is provided for rendering cellulosic material, normally not susceptible to dyes conventionally employed in the dye ing of wool, susceptible to such dyes. In general, this process comprises effecting reaction between cellulose and a monomeric quaternary ammonium compound hava terminal vinyl or CH =C group in the presence of an alkaline catalyst. Preferably, this process comprises pre-treating a cellulose material by impregnating the same in an alkaline medium having a pH of at least 8, and thereafter reacting the alkaline pre-treated cellulose material so as to modify the same with a monomeric quater: nary ammonium compound having a terminal vinyl or CH =C group. Thereafter, the so modified cellulose material is preferably washed free of contaminants and If dyeing is not to take place immediately, the modified cellulose may be dried at a temperature below that which will normally degrade it; and stored.

For purposes of convenience in the present specification, the present process, whereby cellulose materials which are normally not susceptible to dyestuffs of the type conventionally employed in the dyeing of wool, are rendered susceptible, will be termed animalization.

The term cellulose material as it is employed in the present specification, is intended to include natural cellu-' lose materials, as for example, cotton, flax, jute, hemp, sisal, woodlfibers, and regenerated cellulosematerials as for example, cellophane and viscose rayons, such as are normally made by the cuprammonium, nitro-cellulose or viscose processes. In its more preferred sense, as employed in the present process, cellulose material is intended to include cotton and viscose rayon textile materials, including fibers, filaments or formed fabrics there from, and cellophane.

Whether the cellulose material is pre-treated with an alkaline medium having a pH of at least 8, or the reaction between the cellulose and monomeric vinyl quaternary compound is carried out in an alkaline medium having a pH of at least 8, the cellulose material to be animalized should be treated for sufficient time to impregnate it. Complete and uniform impregnation of thematerial is essential to obtaining a uniform modification of the cellulose With the vinyl quaternary compound, and ultimately uniform dyeability. The times and temperatures during which suitable impregnation of the cellulose material is accomplished are, for the most part, inversely proportional. Thus, longer periods of time are required at lower temperatures and shorter periods of time are normally required at higher temperatures. Preferably, the pretreatment, of'for example, cellophane, extends for times of from between about 5 minutes at about 100 C. to about 45 minutes at about 25 C. and more preferably for from about 10 minutes at about C. to about 20 minutes at about 40 C.

The pH of the p-re-treatment bath, or bath containing the alkaline material and quaternary compound, is at least 8 and preferably at least 10, and very effective animalization of cellulose has been carried out by impregnating the cellulose material with mediums having unmeasurably high pH. The alkaline material employed, preferablyin aqueous solutions, may be the preferred alkali metal hydroxides, as for example, sodium hy droxide, potassium hydroxide or lithium hydroxide, as well as other alkaline materials, as for example, sodium carbonate, sodium bicarbonate, choline, morpholine, tri ethanolamine or combinations of these and otherequivalent agents. The important factor in the use of these alkaline materials is that a moderate to strong alkaline material should be employed in order to effect a reaction between the vinyl group of the quaternary compound and the cellulose. T

The effective animalizing agent employed in the process of the present invention must have two essential functional groups thereon, The first is a quaternary group R1 a? X R and the second is at least one terminal vinyl or CH =C group. With respect to the former, the anion component (X-) of this basic group may be halogen, the anion of a water-soluble acid or a hydroxyl group. In accordance with the present invention, it is believe that the susceptibility of the treated cellulosic material to acid dyestuffs is achieved because of widespread and preferably uniform distribution of the quaternary group, which provides basic sites for the acid dye to attach to. The terminal vinyl group is the means by which the quaternary compounds and thus the basic sites of the present invention are durably attached or secured to the, cellulose molecules.

While applicant does not wish, to be bound by any theoretical considerations, it appears that the elfectiveness of the present process results from the quaternay compounds being attached to the cellulose material through an ether oxygen linkage, which linkage results from the saturation of the vinyl group, catalyzed by the presence. of a moderate to strong alkalinematerial. 1 As examples of suitable monomeric quaternary compounds having a terminal vinyl group, the following are illustrative: trialkylorthometa and para-vinyl benzylammonium compounds such as p-vinyl benzyltrimethylammonium chloride; m-vinylbenzyltriethyl-arnmonium hydroxide; trialkylvinyloxycarbonylalkylamrnonium compounds, as for example,

vinyl'oxycarbonylmethyltriethylammonium chloride; 2-vinyloxycarbonylmethyltributylammonium sulfate; the trialkyl-(2-vinyloxyalkylammonium) compounds; (2-vinyloxyethyl)trimethylammonium bromide; (3-vinvyloxypropyl)tripropylammonium sulfate;

the trialkyl(Z-acryloyloxyalkyl) ammonium compounds, as for example,

.(2-acryloyloxyethyl)trimethylammonium chloride; (3-acryloyloxypropyl) -tributylammonium bromide; 2'-acrylamidopropyltr.imethy1ammonium chloride; 4-methacrylamidobutyltrimethylammonium sulfate; 2-vinyl-N-methylpyridinium hydroxide; 4-vinyl-N-propylpyridinium sulfate; 2-vinylphenyltrimethylammonium chloride and 3-vinylphenyltrimethylammonium hydroxide.

In addition to these, the following are illustrative:

Z-methyl-S-vinyl-N-benzylpynidinium chloride; benzyldimethyl-p-vinylphenylammonium bromide; allyldimethyl-p-vinylphenylammoniurn bromide; acryloxyethylbenzyldimethylammonium chloride; acrylamidopropylbenzyldimethylammonium chloride and allyldirnethylphenylammonium bromide.

wherein Y is a member selected from the group consisting of or) R -'NZ-(0Hhn-N-R wherein Z is hydrogen or methyl, n is a digit from 1 to 5, inclusive, X is selected from the group consisting of halogen, the anion of a water-soluble acid or hydroxyl, and R -R are alkyl groups containing from 1 to 4 carbon atoms, and

wherein R is an aliphatic group containing from 1 to 5 carbon atoms and X is as in (A) above, and

wherein X'and R -R are as in (A) above. As examples of. suitable preferred quaternary compounds within the general formula set forth hereinabove, the following are illustrative:

3-acrylamidopropyltrimethylammonium hydroxide; 3-acrylamidopropyltriethylammonium chloride; 4-methylacrylamidobutyltrimethylammonium sulfate; 5-acrylamidopentyltrimethylammonium chloride; 2-vinyl-N-methylpyridinium hydroxide; 2-vinyl-N-ethylpyridinium chloride; l-vinyl-N-methylpyridinium hydroxide; 4-vinyl-N-propylpyridinium sulfate; 5-vinyl-N-n1ethylpyridinium nitrate; 3-vinylphenyltrimethylammonium hydroxide; 2-vinylphenyltriethylammonium chloride; 4-vinylphenyltributylammonium nitrate; l-vinylphenyltrimethylammonium sulfate; 3-vinylphenyltributylammonium chloride and 5-vinylphenyltrimethylammonium acetate.

These and other illustrative quaternary compounds employable in the process of the present invention may be employed singly or in combination with one another.

The quaternary ammonium compounds employa-ble for animalization within the purview of the present invention may be applied to the cellulosic substrate in accordance with techniques normally employable in the respective industries employing such substrates. Since the present invention has particular application in the field of dyeing textile fabrics, the techniques employed in the finishing of textiles will be described more fully in accordance with this aspect of the present invention.

The suitable quaternary ammonium compound may be applied to the pre-treated alkaline-impregnated material or from a suitable alkaline medium by immersion, spraying, padding, or other suitable techniques, and by employing conventional apparatus used in textile finishing and dyeing plants. Because of the large number of finishing and dyeing installations equipped with such apparatus, padding is normally preferred. Employing such technique, an amount of from between about 0.1 and about 15% and preferably between about 3 and about 10% of the quaternary ammonium compound, is applied to the cellulosic textile substrate, based on the dry weight of the textile material. Applications of amounts within these limits appear to provide, for the most part, an adequate number of durable sites for the attachment of the acid dyes and to result inv a material adequately pre-treated to obtain uniform dyeing with such dyes.

Thereafter, the cellulosic substrate may be washed, as with water or mildly acidic baths, such as acetic acid, in order to remove unreacted quaternary ammonium com pounds, alkaline material and other impurities which may interfere with subsequent dyeing operations.

If it is preferred not to dye the material immediately, but rather to store the material, it is preferably dried at temperatures below that which would degrade the modified cellulose. Drying of the pre-treated cellulosic substrate again depends upon the particular material that is being dyed. In the case of textile materials, normally temperatures of less than C. should be employed to avoid degradation of the modified cellulose and quaternary groups.

To the best of my knowledge, any dyes in which the colored ion is the anion, and which are normally employed in the dyeing of wool may be employed. Thus, for example, those dyes termed acid dyes or acid-wool dyes, metallized dyes and mordant dyes, as for example, chrome dyes and the like, may be employed, using the various dyeing procedures and techniques known in the dyeing industry.

Generally speaking, the above dyes are mainly confined into three chemical classes, namely the 2120, anthraquinoid and triarylmethane classes, although other specific classes, such as the azines and xanthenes, provide individually important acid dye materials which may be employed. 7 W W VJ ace /see Name Number Type Acid Yellow 23 azo. Acid Yellow 99.. metallized-azo.

Acid Orange 7. Acid Red 27. Acid Red 18 Acid Violet 30- Acid Violet 3t.-. Acid Blue Acid Blue 45 Acid Blue 120. Acid Blue 161.

Acid Green 25. Acid Green 50.

Acid Black 24 Mordant Yellow 1 Mordant Red 3 Mordant Red 7... Mordant Violet 5... Mcrdant Black 17.-

azo.

azo. metallized-azo.

xanthene.

anthraquinone. triphenylmethane. anthraquinone. azo. metallized-azo. triphenylmethane. anthraquinone. triphenylmethaue.

azo.

azo.

azo chrorne.

azo-chrome. ace-chrome. azo-chrome.

In general, the application of these and other Wooltype dyes may be carried out in accordance with the convenitional wool dyeing techniques or as described in The Theory and Practice of Wool Dyeing, 2nd edition, by C. L. Bird, published by the Society of Dyers and Colorists, England, 1951.

In order that the present invention may be more fully understood, the following examples are given primarily by way of illustration. No details found therein should be construed as limitations on the present invention, except as they appear in the appended claims. All parts and percentages are by weight unless otherwise designated.

Example 1 A strip of cellophane (regenerated cellulose) was soaked for /2 hour in 20 parts of a sodium hydroxide solution. This alkaline solution had an unmeasurably high pH. Two parts of 2-vinyl--I-methylpyridinium hydroxide were added to the soaking bath and the mixture was heated on a steam bath. Heating at 7075 C. was continued for /2 hour, and thereafter the cellophane strip was removed, rinsed and placed in 5% acetic acid solution. This solution was heated gently until discoloration appearing in the cellophane was removed, after which the strip was rinsed several times with water. The amount of the monomeric vinyl quaternary compound applied to the cellophane was 1.5%, based on the dry weight of the cellophane material.

The modified regenerated cellulose was then successfully dyed with a commercial acid dye identified as Calcocid Alizarine Blue SAPG (CI. Acid Blue 45, CI. 63010).

This dyeing procedure was carried out employing a dye bath ratio of 40:1 and a dye concentration of about 1%, employing 1% of sulfuric acid and 10% sodium sulfate. The time and temperature of dyeing was 0.5 hour to the boil of the dye bath solution and retention of the dye bath solution at the boil for one hour. The cello- .phane was successfully dyed a blue color.

A similar strip of cellophane which was not animalized in accordance with the process of the present invention was not successfully dyed.

Example 2 anthraquln one-chrome.

employing the dye and procedure described therein. The cellophane was successfully dyed.

Example 3 A piece of cellophane was soaked in a 10% sodium hydroxide solution for /2 hour at room temperature. Four milliliters of 3-acrylamidopropyltrimethylammonium hydroxide was then added to the pre-treating sodium hydroxide solution and the resulting mixture was heated to 75 C. for /2 hour. The cellophane was removed, rinsed with water and dilute acetic acid, and subsequently rinsed with water again. This treated material had 1.6% of the vinyl quaternary ammonium compound thereon, based on the dry weight of the cellophane. Thereafter, the so treated cellophane was dyed employing the dye and the procedure set forth in Example 1 hereinabove.

Example 4 A strip of cellophane was placed in a solution consisting of 5 parts of paravinylphenyltrimethylammonium sulfate, 10 parts of water and 10 parts of a 10% potassium hydroxide solution. The resulting mixture was heated to C. for 30 minutes. Thereafter, the cellophane was removed, washed with water and acetic acid, and subsequently washed again.

The modified cellulose was then successfully dyed in accordance with the procedure set forth in Example 1.

Example 5 A skein of viscose rayon was pre-treated with a sodium hydroxide solution in accordance with the procedure set forth in Example 1 and modified with the vinyl quaternary ammonium compound described therein. The modified viscose rayon skein was then washed several times with water and acetic acid and successfully dyed in accordance with the procedure set forth in Example 1. A skein of viscose rayon, not modified in accordance with the present invention, could not be dyed employing the same dye and procedure.

Example 6 A sample of 80" x 80" cotton was pro-treated in accordance with the procedure outlined in Example 1 and modified with 4-methylacrylamidobutyltriethylammonium chloride, employing the procedure outiined therein. The treated sample was subsequently washed with water and acetic acid and washed again preparatory to dyeing. The dyeing procedure outlined in Example 1 was followed and the modified fabric was successfully dyed.

80" x 80 cotton fabric not modified in accordance with the procedure of the present invention was not dye able employing the dye and procedure of Example 1.

In accordance with the process of the present invention, it is preferred to pre-treat the cellulosic material with a suitable alkaline medium prior to modification with the monomeric quaternary vinyl compound. This is so in that this method appears to improve the dyeability of the material. However, in accordance with the present invention, and as illustrated by the above examples, the pretreatment with an alkaline medium and the modification with a monomeric quaternary vinyl compound may be carried out substantially simultaneously, preferably while employing longer times and higher temperatures.

It will be readily noted that the present invention provides means whereby cellulose materials such as textile fabrics may be pre-treated, subsequently blended with wool fibers, and then successfully dyed in a single dyeing operation. Other modifications along this line will readily suggest themselves to one skilled in the art.

I claim:

1. A process for animalizing cellulose base materials which comprises eifecting reaction between cellulose and a monomeric quaternary ammonium compound having a vinyl group of the formula CH =C in the presence of -7 an alkaline catalyst, pre-treating the cellulose material by impregnating it with an alkaline medium having a pH of at least 8 and reacting said alkaline-impregnated material with a monomeric quaternary compound having a vinyl group of the formula CH =C 2. A process for animalizing cellulose base materials which comprises pre-treating the cellulose material by impregnating it with an alkaline medium having a pH of at least 8 and reacting said alkaline-impregnated material with a monomeric quaternary compound having a vinyl group of the formula CH =C 3. A process according to claim 2 in which the monomeric quaternary compound is applied in an amount sufiicient to add on from between 0.1 and 15% solids, based on the dry weight of the cellulose material.

4. A process according to claim 2 in which the pH of the alkaline medium employed in the pre-treatment of the cellulose material is at least 10 and the alkaline material employed is an alkali metal hydroxide.

5. A process according to claim 2 in which the cellulose material is cellophane.

6. A process according to claim 2 in which the cellulose material is viscose rayon.

7. A process according to claim 2 in which the cellulose material is cotton.

8. A process for dyeing cellulose textile material with dyes normally employed in the dyeing of wool, which comprises impregnating the cellulose material with an aqueous medium containing sodium hydroxide and having a pH of at least 10, modifying said textile material by reacting it with from between 0.1 and by weight, based on the weight of the dry cellulose material, of a monomeric quaternary compound having a vinyl group of the formula CH =C and thereafter dyeing said modified cellulose with a wool dye.

9. A process for animalizing cellulose base material which comprises eifecting reaction betweenthe cellulose base material and a monomeric quaternary ammonium compound having a vinyl group of the formula CH =C in the presence of an alkaline catalyst and at a pH of at least 8.

10. Animalized cellulose base material comprising cellulose base having reacted therewith a monomeric 8 quaternary ammonium compound having a vinyl group of the formula CH =C 1 11. A process for treating cellulose base material which comprises efiecting reaction between said base material and a compound having the formula CH =CH-Y in which Y is a member of the group consisting off wherein each of R R and R are alkyl radicals containing from 1 to 4 carbon atoms, R is an' aliphatic radical containing from 1 to 5 carbon atoms, Z is a member of the group consisting of hydrogen and the methyl radical, n is a whole number from 1 to 5 inclusive and X is selected from the group consisting of halogen, the anion of a water-soluble acid, and hydroxyl, in the presence of an alkaline catalyst and at a pH of at least 8.

l2. Animalized cellulose'base material comprising a cellulose base having reacted therewith a compound having the formula CH =CH--Y wherein Y is a member of the group consisting of (A), (B)' and (C) as defined in claim 11.

References Cited in the file of this patent UNITED STATES PATENTS James June 1, 1954 

1. A PROCESS FOR ANIMALIZING CELLULOSE BASE MATERIALS WHICH COMPRISES EFFECTING REACTION BETWEEN CELLULOSE AND A MONOMERIC QUATERNARY AMMONIUM COMPOUND HAVING A VINYL GROUP OF THE FORMULA CH2=C< IN THE PRESENCE OF AN ALKALINE CATALYST, PRE-TREATING RHE CELLULOSE MATERIAL BY IMPREGNATING IT WITH AN ALKALINE MEDIUM HAVING A PH OF AT LEAST 8 AND REACTING SAID ALKALINE-IMPREGNATED MATERIAL WITH A MONOMERIC QUATERNARY COMPOUND HAVING A VINYL GROUP OF THE FORMULA CH2=C<. 